Apparatus for separating the constituents of gaseous mixtures



' 1,619,169 Mrch 1 1927' c. c. VAN NUYS APPARATUS FOR SEPARATING THE CONSTITUEJNTS OF GASEOUS MIXTURES Original Filed Sept. 9. 1920 INVENIOR \D' BY 12 g 'ofi A4 ATTORNEY s Patented Mar. 1, 1927.

CLAUDE O. VAN NU'YS, OF CRANFORD, NE COMPANY, INCORPORATED, OF NEW YOIR w Jnnsnx, as'sronoa r am .nnnucrron' x, N. Y., a oonronar'rou or new YORK.

APPARATUS FOR SEPARATING THE CDNS'IITUEKTSDF GASEOUS MIXTURES.

Original mime... nled'september a, 1920, serial no. 409,096. Divided and um application m December 6, 1924.

This invention relates to the liquefaction and separation of the constituents of gaseous mixtures, and isparticularly applicable to therecovery of oxygen and nitrogen from the atmosphere, although the princi les hereinafter describedmay be employe in separating the constituents of gaseous mixtures other than air. 1

This application is a division of application Serial No. 409,096, filed Sept. 9,1920, now Patent No. 1,539,528.

Separation of the constituents of a binary gaseous mixture is accomplished in accordance-with a well known method by compression and cooling of-the mixture, followedby a liquefaction in two fractions, at a pressure somewhat below the initial pressure of the mixture. The first liquid fraction is ob tained b a selective condensation in a tubuar con enser employing the principle of backward return so as to obtain a liquid enriched in the less volatile constituent to which is added sufiicient unenriched liquefied mixture, obtained from a separate condenser called the liquefier. to make up for losses due to'heat leakage.

The second fraction consisting substantially of the more volatile constituent delivered at the top of the backward return tubular condenser is, after it has been liquefied by indirect contact with liquids accumulated at the bottom of the rectification column, delivered to the rectifier at a level somewhat higher than the level at which the liquid constituting the first fraction enters the rectifier. This second liquid fraction is expected to wash the less volatile constituent from the ascending vapors by reciprocal evaporation and condensation, and to thus permit liquefaction of that constituent in a substantially pure condition.

In the normal operation of such a method, an efliue'nt gas is obtained which contains, amounts of the more easily condensible constituent of the original gaseous mixture to be separated far in excess of the theoretic minimum, and the escape of this constituent; in the efliuent gas represents a serious loss of efficiency of the method. The resulhde-f be scribed may be explained by reference tothe}. application of the prior method to the sep' aration of the constituents oxygen and mm;

, gen from the atmosphere.

Serial No. 754,281.

uid obtained at the bottom of the condenser lace is sufliciently efficient so that the un-' is a-liquid of maximum possible degree of enrichment in oxygen, at is, it 1s that liquid which will be in phase equilibrium with the gaseous mixture tom of the condenser. Under these conditions, it is clear that the amount of unlique-.

nitrogen leaving the top of the cona maximum. If the composition in oxygen of the enriched liquid constituting 1" fied denser is the first fraction is less than the limit comentering the bot-" position just specified, then the amount of the second fraction, i. nitrogen leaving the top denser, will be less. In the normal opera: tion of this method, the attemptis generally made to produce an bottom of the tubular leaving the top stituting ultimately the second li' uid fraction is ust sufficient to deprive t e vapors ascending at the level in therectification 001-.

umn at which the first liquid fraction'is delivered thereto of the oxygen contained in those Vapors.

This being the case, it is clear that the advantage of the max: ossible degree of oxygen'fenrichment f. a

with the principle backward return. on the contrary, this enrichment is carried on'f method fails to take imum attaina of" condensation by le in accordance enriched. liquid at the condenser whose com position is such that the amount of nitrogen" of the condenser and cone., theunliquefiedf of the tubular con-j only to that point where the amount of; un-fr j liquefied nitrogenis most suitable for the'f', requirements. of the subsequent rectification.

Due, however, to unavoidable variations in quantity and compositlon ofthe enriched .hquid obtained at the bottom of the condenser by r-eason of. variations of operating -condition s,fand further by reason of the fact thatatmospheric air is not asimple'binarfi" mixture, the consequences of which fact wi noted presently, it is he operation of this method, in order to insure proper rectification and obtain substan tially pure oxygen, to evaporate and cause to ascend in the column an excess .ofoxygen I found necessary in ture an the rare elements, helium, neon,

: xenon and krypton, substantially 1% of argon,'of which the saturated vapor ressure corresponding to any temperature 18 intermediate between those of oxygen andnitrogen at the correspondin temperature In fact, the boiling point 0 -argon at ordinary pressures is only 3 to 4 degrees lower than that of oxyfigen. Hence, when air is selectivel lique ed with backward return, we shou d expect to find the major portion of the argon thereof contained in the liquid fraction, the argon content of this liquid increasing as the liquefied fraction of the air is increased. If all the argon resent in air was contained in the enriche liquid, then assuming that this argon is not subsequently removed, it would be impossible to obtain oxygen of a purity greater than about since the ar on, being 1% of the whole mixture, woul be ap roximately 5% of the oxygen contained tierein. Actually, however, ar on will be present both in the enriched liquid delivered at the bottom of the tubular condenser and in the unliquefied residue leaving the top thereof, and the amount of argon leaving the top will be greater according as theamount of nitrogen drawn therefrom is greater. It IS clear, therefore, that it will be of advantage to carry the oxygen enrichment of the liquid condensed in and obtained at the bottom of the tubes to the maximum possible degree.

An object of the present invention is the provision of an apparatus for rectifying liquefied gases to separate the constituents of gaseous mixtures represented thereby in an improved, economical and eilicicnt manner, and permitting the recovery of a large portion of the energy originally employed in raising the gas to its initial pressure.

The objects and advantages of the invention will be apparent as it is better understood by reference to the following specification and accompanying drawing in which an apparatus which is capable of use in connection with the method is diagrammatically illustrated. The details of the apparatus may be Widely varied, and no attempt has been made to illustrate such details and thereby obscure the purpose of the drawing, The difliculties heretofore experienced in the separation of gaseous mixtures by liques.w

faction and rectification as a ove noted, may be overcome-to a-large degree by the delivery to the rectification column 0 a regulated quantity of a liquid obtained by liquefying onlyfia part of the residual gas drawn from the top of the backward return condenser.

guantities of carbon dioxide, mois-' This portion of the residual gas is liquefied while still under the condenser pressure by passing it through a coil surrounded by li u1d s accumulating at the base of the recti cation column an then, after its pressure has been released by a' reducing valve to that of the rectifier, it is employed therein as a clarify ng l1 uid, and thus there is left available a consi erable amount of the residual gas at the original pressure prevailing in the tubular condenser. Y y

' The relatively high pressure residual gas, after its temperature has been raised to any desired point by heat interchange with the incoming mixture,- may be profitably employed in an expansion engine or turbine to assist im the necessary refrigeration of the system,j-'as;f 'we1l as to recover a portion of t 1e energy originally expended in raising the pressure of the mixture to the point necessary for operation of the cycle. A considerable portion of the argon content of the orig-. inal air will be eliminated with the residual gas, rendering it possible to attain a higher purity of oxygen at the base of the rectification column with less loss of oxygen in the efiluent gas leaving the top of the column.

In carrying out one embodiment of the method, air for example, compressed and cooled in the customary manner, is delivered to a column in which it is subjected to indirect contact with colder liquid or aseous products, and the ortion of the air t us liquefied is permittc to return in contact with further quantities of air and to accumulate in the bottom of the column. Preferably, though not necessarily, this liquid is subjected during its backward passing to a partial rectification by contact with the incoming air for the purpose of insuring that the '1 liquid will contain the maximum quantity of oxygen possible, this being substantially 47% or a composition which is in phase equilibrium with the incoming air. During its upward passage, the air is cooled sufficiently by indirect contact with the cold liquid orgaseous products to separate all of the oxygen and a portion of the nitrogen sothat the residual unliquefied gas is substantially nitrogen, a portion which is liquefied and utilized as a clarifying liquid in the rectifier while the balance is available for the purposes noted.

The accumulated liquid consisting principally of oxygen and nitrogen, the oxygen being in proportion of approximately 47%, is then delivered to the rectifying compartment through a reducing valve which permits the reduction of pressure and the low temperature necessary in order that liquid oxygen collecting at the bottom of the rectifier may liquefy selectively the incoming air by indirect contact therewith, and be vaporized thereby. The liquid is delivered to the middle part of the rectification column and thereby accomplish and the li uid finally in the accumulating in the lower liqui compartmentis substantiall ized in cooling ad itiona quantities of the comcfiressed air. The vaporized oxygen may awn oil at a substantial pressure and after being warmed by heat interchange with the incoming air, it may be expanded a suitable en e to recover another port on of the worg drigin y expended m raising the air to its imtial pressure. The vapor passing r lower. partjof the rectifier contains a substantial proportion of oxygen, and to preventthe esca of the major portion of this oxy-v thereby increase the efliclency of.

gen an rectification the proper proportlon of hgua;

- fied residual gas or nitrogen is delivere v the upper fplart of the rectifier where it serves as a clari ing liquid to wash substantially all of the oxygen from the ris1ng vapors. The efiluent vapors leaving the rectifier and consistin substantially of nltrogen may be expande after heat interchange with the incoming air to recover energy originally expended in compressin the air, v

The argon content 0 the enriched liquid constituting the first liqu1d fraction, being by the operation of this method less than'in the case where the oxygen ,enrichment of this liquid is carried to a less degree, the

rectification of this liquid may be accomplished without it being necessary to vaporize and pass upward in the column as large an amount of oxygen to'prevent the oxygen purityat the base of the column becoming reducedby the presence of argon; Although the argon percentage of the clarifying hquid dc greater .in this method than in the prior method. described, the actual .amount of argon in the liquid state delivered to the top of the column will be considerably less -'-in absolute amount since only a portion of the residual gas delivered at the top of the use as clarifying liquid. Thus the method,

backward return condenser isliquefied for l in addition to possessing the advantage of reducingethe' actual amount of argon necesfurther-advantage of orci gon passingthrough the rectlficatlon column sary to eliminated in the rectification column from the oxygen roduct, possesses the the actual ar-.

to-concentr'ate toward the upper regions of said column and thus to increase its tend ency to elimination with the efiiuent gas.

A further advantage of the method lies in the fact that the amount of clarifying liquid delivered to the tqlp of the column may be regulated indepen ently of the amount of .enriched liquid produced in thei"backward oxy en which is vaporupwardly from the a reducing valve 19 to trays 20 of usual form, do 21 disposed between the lower trays and return condenser and thus this regulation may be adapted more closel to the re uire- 'ments of the enriched liqui and the a just- I original pressure of the backward return condenser. I

With this brief description of the method of operation, the apparatus and mode of applying the invention will be more clearly unerstood with relation to the drawing which illustrates diagrammatically an apparatus for use in practicing the invention. It is to be understood, however, that the method and apparatus are of general application and that no limitation is implied, therefore, by reference to the atmosphere or to the particular apparatus illustrated. In the drawing, 5 indicates a column havin a liquid pot 6, a rectifying compartment a refrigerating chamber or liquefier 8, a liquid compartment 9 in which a liquid receptacle 10 is suspended, and upper and lower rectifying chambers 11' and 12. Cold compressed gas is delivered to the pot 6 through a pipe 13 and lpasses thence through the trays 14, on whic liquid accumulates for the purpose of separating any excess of. nitrogen from this liquid. The gaseous mixture passes thence through tubes 15, which extend through the gas chamber 8, liquid compartment 9 and receptacle 10 to a head 16. Nitrogen is withdrawn from the head through a pipe 17.

- The liquid accumulating in the pot 6 is deivered at the top of the column 1slivered therefrom through a pipe 18 having the lower rectifying compartment 11 where it and also in a receptaprovided with a coil22, one end ofwhich is connected to the pipe 17 while the other communicates with a pipe. 23'having a reducing valve 24, which delivers the nitrogen liquefied inthe coil to the upper compartment of the rectifier. The liquid nitrogen passes accumulates on downwardly over trays 25 and joins the liquid delivered through the pipe 18.

The liquid accumulating in the compartment 9 is substantially pure oxygen, and as the liquid is evaporated by indirect contact with the gaseous mixture in the tubes 15 the oxygen is withdrawn through a pipe 26. Vapors arising from the receptacle 10 pass upwardly through the trays 20 and 25 in direct contact,-first, with the liquid delivered through the pipe 18, and then with the liquid nitrogen delivered through the pipe 23. In the rectifying compartment, the oxygen in the vapor is iqueiied and 10lDS the downwardly flowing liquid. Nitro en is at the same time se arated from the ownwardly flowing liquid and thus the effluent gas from the rectifier becomes substantially pure nitrogen. By proper regulation and control of the amount of liquefied nitrogen delivered to the rectifier, it becomes ossible to separate a greater proportion of t e oxygen from the incoming air than has heretofore been practicable.

To insure proper transfer of cold from the outgoing gases to the incoming gaseous mixture, an exchangerof temperature is em ployed comprising aplurality of compartments A, B, C and D, each compartment being divided by bafiies 28, to cause the air to circulate therein about two sets of pipes 29 and 30, through which the gases escaping from the column are conveyed. The nitrogen, for exam le, escaping through the pipe 17, is, with t e exception of that portion which passes through the coil 22, delivered to a compartment 31 at one end of the section D of the exchanger and passes thence through tubes 29, communicating with the compartment, to a compartment 32 at the other end of the section. The nitrogen is delivered by a pipe 33 to a corres onding compartment 34 of the section (J and passes through tubes 29 therein to a compartment 35. Thence the nitrogen is conveyed through a pipe 36 to a compartment 37 at one end of the section B of the exchanger, passes through the tubes 29 of the exchanger to a. compartment 38, thence through a pipe 39 to a compartment it) at the end of the section A of the exchanger wherein it is conveyed through tubes 29 to a compartment 11. From the compartment 41, the nitrogen is withdrawn through a pipe 42 having a controlling valve 43 and is delivered to the expansion engine 44: where it is expanded with external work and the temperature is accordingly reduced. From the engine the expanded gas is delivered through a pipe 45 to a compartment 46 at one end of the section B of the exchanger. Thence the gas passes through tubes 30 to a compartment 47 between the section A and B. Tubes 30 in the section A convey the expanded gas to a compartment 48 at the end of the section A to which an outlet 50 for the nitrogen is con nected. The nitrogen is delivered at substantially atmospheric temperature and pres sure and may be stored for utilization in any suitable manner.

The oxygen delivered from the column through the pipe 26 enters a compartment 51 at the end of the section D of the exchanger and passes through the tubes 30 in the several sections thereof to a chamber 52 at the end of the section A whenceit is delivered through a pipe 53 having a controlling valve 54 with engine 55 where the oxy en is expanded with external work an thereby cooled. From the engine 55 the expanded oxygen is delivered throu h a pipe 56 to a pre-cooler 57 consisting o a shell 58 and a bundle of tubes 59 about which the incoming air circulates, the air being introduced through a pipe 60 and delivered through a pipe 61. The oxygen from the pipe 56 passes through a bundle of tubes 59 and is delivered through a pipe 62 at substantially atmospheric pressure and temperature and may be stored for suitable use.

The eflluent gas from the rectifier is delivered by the pipe 27 to a compartment 63 of the section D of the exchanger and passes thence through tubes 30 to a compartment 64 whence it travels through'tubes 30 in the section C of the exchanger to a compartment 65. From this compartment the gas is withdrawn and is delivered by a pipe 66 to an expansion engine 67 where the gas is expanded with external work and is consequently cooled. From the engine 67 0. pi e 68 conveys the gas to the chamber 8 in t e column where the gas circulates about the tubes 15 and serves to cool the incoming air and liquefy portions thereof. From the compartment 8 the gas escapes through a pipe 69 to a compartment 70 at the end of the section D of the exchanger and is delivered thence through tubes 30 in the sections C and D of the exchanger to a compartment 71. A pipe 72 conveys the gas to a compartment 73 at the end of section B of the exchanger, and the gas is delivered thence through tubes 30 in the sections A and B to a compartment 74, the as escapin throu h a pipe 75, controlled by a valve 6 at su stantially atmospheric pressure and temperature. A portion of the efiiuent gas may be withdrawn from the pipe 72 through a pipe 7 6 controlled by a valve 77, which delivers the gas to the pro-cooler 57. Thus the precooling of the air may be regulated as desired. The gas thus delivered to the precooler escapes through av pipe 78, and may:

be stored for utilization.

It is to be understood that cooling of chamber 8 may be accomplished by del1ver-' ing cold expanded nitrogen thereto instead of the expanded etiiuent gas. In this event, the cold of the expanded etlluent gas will be utilized in the exchanger, the change requiring merely a slight rearrangement of the gas conveying pipes. As previously noted,

the disposition of the cold expanded gases will depend more or less on the relative volumes thereof which are available.

The air cooled in the pre-cooler is deliv-' ered by a pipe 61 to a compressor 79, where it is compressed and delivered through a pipe 80 to a water cooler 81. Thence the compressed and cooled gas is delivered through a pipe 82 tothe section A of the exchanger j where it travels about the bafiies 28, and is delivered through-pipes 83, 84, and 85, to

"the successive sections of the exchanger ration of the constituents of the gaseous mixwhere the cooling is completed. The air finall passes from the exchanger through the pipe 13 to the pot 6 at the bottom of the column.

Assuming, therefore, thatthe apparatus is in operation, it'will be seen that the cooled compressed gas is successively sub'ected to the cooling influence of cold expan ed ases and accumulated liquid, and that the hquid fraction resulting is rectified to produce a liquid as rich in oxygen as is possible under commercially without further treatment} The provision of a regulated supply of liquid nitrogen for rectification purposes not only provides more eflicient rectification and sepature, but it facilitates regulation and per- 7 mits balancing the operation in such a I not with a minimum of attention. Separal? as to insure a maximum output of the pr tion of the constituents ofthe gaseous mixture is accomplished at a pressure only slightly below the initial pressure to which the as is raised, and the products escape at the initial pressure, or the pressure of separation. The expansion of-the products following liqfiiefaction. and after these prod-- ucts have een warmed by contact with the incoming air, insures the recovery of a large proportion of the energy consumed in raising the gaseous mixture to its initial pressure. The energy recovered may be employedin compressing further quantities of gas with such additions ofenergy as are requisitegtp provide the necessary pressure.

I tion since it is self-cooling to a marked degree, and consequently it is necessary mereliy to start compression and to direct the pro The apparatus is readily placed in operaucts of expansion in the engines to the Q proper points to quickly decrease the temperature of the apparatus and accumulate vscribed. a From the foregoing description, it

a body of liquid therein. Thereafter the operation is substantially automatic as dee111 be apparent that the method recited in the {present application as well as the apparatus adapted for use therein, marks a distinct forward ste in the art of separating gaseous mixtures.

t becomes possible thereby to provide a much closer and more eflicient separation of the constituents'of a gaseous mixture, and to recover both constituents in a substantially pure condition.

Various changes may be made in the details of the apparatus, Without departing from the invention or sacrificing anyof the advantages thereof.

I claim:

1. In an apparatus for separating the constituents of a aseous mixture'by liquefaction, the combmationof a column having a plurality of tubes for the passage of the mixture, a chamber surrounding the tubes to receive liquid, 3. head in which the tubes terminate, means for withdrawing residual unliquefied gas from the head, means for non-selectively liquefying a regulated portion of the residual gas thus withdrawn, means for diverting the remainder of the re sidual gas from the liquefying means,a rectifying compartment and means for delivering liquid produced in the tubes and the liquefied residual gas to the rectifying compartment.

2. In an apparatus for separating the constituents of a gaseous mixture by liquetartion, the combination of a column having a plurallty of tubes for the passage of the terminate, means for withdrawing residual unliquefied as from the head, means for non-selective y liquefying a regulated portion of the residual gas thus withdrawn, means for diverting the remainder of the residual gas from the liquefying means, a rectifying compartment, means for delivering liquid roduced in the tubes and the liquefied resldual gas to the rectifyin compartment, and means for utilizing t e remainder of the unliquefied residual gas for the recovery of energy therefrom.

3. In an apparatus for separating the constituents of a gaseous mixture by liquefaction, the combination of a colum n having a .plurality of tubes for the passage of the 'mixture, a chamber surrounding the tubes rectifying compartment, means or delivering llquid produced in the tubes and the liquefied residual gas to therectifying compartment, an exchanger of temperature wherein the remainder of the unliquefied residual gas is'warmed by indirect contact with the lncoming mixture and an engine in which the residual gas is expanded.

4. In an apparatus for separating the constituents of a gaseous mixture by liquefaction, the combination ofa column having a plurality of tubes for the passage of the mixture, a chamber surroundin the tubes to receive liquid, at head in whim the tubes terminate, a pipe for Withdrawing the re- 5 siduul unliquefied gas, a reetifylng compartment, a coil in said compartment and connected to the pipe to non-selectively liquefy a regulated portion of the residual gas,-means or diverting the remainder of the residual gas from the coil and means 10 for delivering liquid produced in the tubes and coil to the rectifym compartment.

In testimony whereof afiix m signature.

CLAUDE 0. VA NUYS. 

